KR20100098367A - Thermoplastic resin composition and molded body obtained by molding the same - Google Patents

Abstract

The thermoplastic resin composition WHEREIN: The silane which has 100 mass parts of polylactic acid-type resin or polylactic acid-type resin composition, 0.01-10 mass parts of peroxides, and 2 or more functional groups selected from an alkoxy group, an acryl group, a methacryl group, and a vinyl group. It is obtained by mix | blending 0.01-5 mass parts of compounds. The polylactic acid resin composition may contain 90 to 99.5 mass% of polylactic acid resin and 0.5 to 10 mass% of a plasticizer. The thermoplastic resin composition may further include a fibrous reinforcing material, a polyvalent carbodiimide compound, and a flame retardant as necessary.

Description

Thermoplastic resin composition and molded object formed by this {THERMOPLASTIC RESIN COMPOSITION AND MOLDED BODY OBTAINED BY MOLDING THE SAME}

The present invention relates to a thermoplastic resin composition and a molded article formed by molding the thermoplastic resin composition.

As a raw material for molding a molded article, generally, polypropylene (PP), acrylonitrile butadiene styrene copolymer resin (ABS), polyamide (PA6, PA66), polyester (PET, PBT), polycarbonate (PC), etc. Resin is used. However, moldings made of such resins are excellent in formability and mechanical strength, but they increase the amount of waste at the time of disposal and remain semi-permanently in the ground even when buried because they are not decomposed mostly in the natural environment. Moreover, these resins are resins using petroleum as a starting material, and have a large environmental load throughout the life cycle.

On the other hand, in recent years, from the standpoint of environmental conservation, resins using raw materials derived from plants including polylactic acid have attracted attention. Among them, polylactic acid is one of the resins having the highest heat resistance, and since it can be mass-produced, its price is low and its usefulness is high. In addition, polylactic acid can be produced by using plants such as corn, sweet potato, etc., which can contribute to saving of depleted resources such as petroleum.

However, even when there are polylactic acid having high heat resistance among resins made of plant-derived raw materials, when the crystallinity is low, it is still hard to say that the heat resistance is still low compared to ABS and polyester, and it has sufficient heat resistance to withstand practical use. . Generally, it is said that the temperature which can endure practical use is 50-70 degreeC indoors, and 90 degreeC in vehicle installations, such as a car. In consideration of safety in use, durability to an ambient temperature of 100 ° C is practically required. Although polylactic acid is a crystalline resin and has a low crystallization rate, crystallization does not proceed within the same time as the mold cooling time in the injection molding process of general-purpose plastics such as PP described above, and the heat resistance is around 60 ° C. In order to improve heat resistance, there is a method of adding a nucleating agent such as talc to polylactic acid and increasing the crystallization rate by increasing the crystallization rate during polylactic acid molding. Nevertheless, however, in order to advance the crystallization, it is necessary to take a long time to cool the mold.

In order to solve the above problem, a method of improving the crystallization rate by combining a crosslinking agent such as a peroxide and a crosslinking aid such as an acrylic ester and efficiently introducing the crosslinked structure into the polylactic acid has been proposed (JP2005-232225A). It is discovered that the crystallization rate can be significantly increased by further blending specific plasticizers (WO2007 / 049529).

However, it is still insufficient in terms of molding cycle, and there is a problem that the hot stiffness is not sufficient even if the polylactic acid is crystallized. Hot stiffness refers to a measure of how hard it is to deform with respect to a load applied in a high temperature environment. For example, the heat distortion temperature (DTUL) of the crosslinked polylactic acid is 100 ° C. or more when measured under a condition of a maximum stress of 0.45 MPa, but is about 60 ° C. when measured under a high load condition of 1.8 MPa. Therefore, heat resistance cannot be sufficient in the use | work which takes high load under high temperature, and the large molded article which becomes heavy in the weight of the product itself. In addition, in order to advance the crystallization of polylactic acid in injection molding, it is necessary to increase the mold temperature to near the crystallization temperature. However, since polylactic acid has low hot rigidity at its crystallization temperature, when the resistance is large at the time of releasing, there is a problem that high pressure is applied by the ejector pin and eventually deforms.

In order to solve the problem of hot rigidity, there is also a method of blending inorganic reinforcing materials such as glass fiber and talc. For example, in JP2006-176652A, a composition obtained by blending glass fibers with crosslinked polylactic acid is shown. With this composition, the crystallization rate is improved as compared with the conventional polylactic acid, and the problem of hot rigidity is also considerably improved. However, compared with general-purpose resin, it is hard to say that it is still enough in performance.

In addition, polylactic acid is low in comparison with glass fiber reinforced polyamide (PA + GF) in terms of strength, and thus cannot be said to have practical strength that can be substituted for PA + GF. In recent years, miniaturization of products such as mobile phones and small notebooks has progressed, and resin parts such as exteriors are required to be thinner, and the use ratio of PA + GF with high rigidity is increasing. About polylactic acid, if not only rigidity but also intensity | strength are not high enough, the problem of a crack easily arises. The strength of glass fiber reinforced polylactic acid (PLA + GF) is similar to that of PA + GF.

The present invention aims to solve the above problems, and aims to increase the crystallization rate of polylactic acid and improve the hot stiffness to further improve the strength.

In addition, the present invention provides a resin composition and a molded article for improving handling properties in production, improving heat resistance due to crystallization of polylactic acid, and improving handling properties during molding, such as shortening the take-out time of a product during molding. To provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve such a subject, as a result of the careful examination, the present invention is based on a resin composition containing a polylactic acid resin, a peroxide, and a specific silane compound, or on a resin composition further containing a fibrous reinforcing material and a carbodiimide compound. It was found that the above object is achieved. That is, the summary of this invention is as follows.

(1) 0.01-silane compound which has 100 mass parts of polylactic acid-type resin or polylactic acid-type resin composition, 0.01-10 mass parts of peroxides, and 2 or more functional groups chosen from an alkoxy group, an acryl group, a methacryl group, and a vinyl group. It is obtained by mix | blending 5 mass parts, The thermoplastic resin composition characterized by the above-mentioned.

(2) The thermoplastic resin composition of (1), wherein the polylactic acid resin composition includes 90 to 99.5 mass% of polylactic acid resin and 0.5 to 10 mass% of a plasticizer.

(3) The plasticizer is at least one selected from aliphatic polyhydric carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, and aliphatic polyether polyhydric carboxylic acid ester derivatives. Thermoplastic resin composition.

(4) at least one member selected from organic amide compounds, organic hydrazide compounds, carboxylic acid ester compounds, organic sulfonates, phthalocyanine compounds, melamine compounds and organic phosphonates as crystal nucleating agents. The thermoplastic resin composition of any one of (1)-(3).

(5) The nucleating agent is 5-sulfoisophthalic acid dimethyl metal salt, N, N ', N "-tricyclohexyltrimesinic amide, N, N'-ethylenebis (12-hydroxystearic acid) amide, octane dicar The thermoplastic resin composition of (4), characterized in that at least one member selected from acid dibenzoylhydrazide.

(6) The thermoplastic resin composition according to any one of (1) to (5), wherein the polylactic acid resin has polylactic acid as a main component.

(7) The thermoplastic resin composition according to any one of (1) to (6), wherein the polylactic acid resin is made of a plant-based raw material.

(8) 100 mass% of the whole, 39.9-89.9 mass% of thermoplastic resin compositions in any one of (1)-(7), 60-10 mass% of fibrous reinforcing materials, and polyhydric carbodiimide compound O.1-10 It contains mass%, The thermoplastic resin composition characterized by the above-mentioned.

(9) 100 mass% of the whole, 36.9-86.9 mass% of thermoplastic resin compositions in any one of (1)-(7), 10-60 mass% of fibrous reinforcement materials, 3-30 mass% of flame retardants, and polyhydric carbon 0.1-10 mass% of body imide compounds, The thermoplastic resin composition characterized by the above-mentioned.

(10) The thermoplastic resin composition of (8) or (9), wherein the fibrous reinforcing material is a glass fiber having a flat cross section.

(11) A molded article characterized by molding the thermoplastic resin composition of any of the above (1) to (10).

(Effects of the Invention)

According to the present invention, a thermoplastic resin composition and a molded article having excellent heat resistance, strength and moldability and low dependence on petroleum products are provided. This molded article can be applied to injection molded articles and the like, and since biodegradable resins derived from natural products are used, they can contribute to saving of depleted resources such as petroleum.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The thermoplastic resin composition of the present invention is a polylactic acid resin (A), a peroxide (B), a silane compound (C), a plasticizer (D), a crystal nucleating agent (E), a fibrous reinforcing material (F), and a polyvalent carbodiimide compound (G). ) And flame retardant (H) as a component.

As polylactic acid-type resin (A) used by this invention, poly (L-lactic acid) and poly (D-lactic acid) are mentioned. In addition, these may be used as a main component and polyglycolic acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate terephthalate, polybutylene succinate terephthalate or the like may be mixed. From the viewpoint of petroleum resource saving, a plant-derived raw material is good, and among them, it is preferable to use poly (L-lactic acid), poly (D-lactic acid), and mixtures or copolymers thereof in terms of heat resistance and moldability. It is preferable to mainly use poly (L-lactic acid) from a biodegradable viewpoint.

The polylactic acid mainly composed of poly (L-lactic acid) has a different melting point depending on the proportion of the D-lactic acid component. In the present invention, in consideration of the mechanical properties and the heat resistance of the molded article, the melting point of the polylactic acid is preferably 160 ° C or higher. In polylactic acid mainly containing poly (L-lactic acid), in order to make melting | fusing point 160 degreeC or more, it is suitable to make the ratio of a D-lactic acid component less than about 3 mol%.

It is preferable that the melt flow rate in 190 degreeC of polylactic acid-type resin (A) and load 21.2N is 0.1-50 g / 10 minutes, It is more preferable that it is 0.2-20 g / 10 minutes, 0.5-10 g Most preferred is / 10 minutes. When melt flow rate exceeds 50 g / 10min, melt viscosity may become very low and it may be inferior to the mechanical characteristic and heat resistance of a molded object. On the other hand, when melt flow rate is less than 0.1 g / 10min, load may become very high at the time of shaping | molding process, and operation property may fall.

The polylactic acid-based resin (A) is usually produced by a known melt polymerization method or by further using a solid phase polymerization method. A method of adjusting the melt flow rate of a polylactic acid resin (A) to a predetermined range, wherein when the melt flow rate is very high, a small amount of chain length extender such as a diisocyanate compound, a bis oxazoline compound, an epoxy compound, an acid A method of increasing the molecular weight of the resin using anhydrides or the like can be used. In contrast, when the melt flow rate is very low, a method of mixing with a biodegradable polyester resin or a low molecular weight compound having a high melt flow rate may be used.

Although it does not specifically limit as a plasticizer (D) used for this invention, What is excellent in compatibility with polylactic acid-type resin (A) is preferable. Examples thereof include aliphatic polyhydric carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxy ester derivatives, aliphatic polyether derivatives, aliphatic polyether polyhydric carboxylic acid ester derivatives, and the like. Specific compounds include glycerin diaceto monolaurate, glycerin diaceto monocaprate, polyglycerin acetic acid ester, polyglycerol fatty acid ester, medium chain fatty acid triglyceride, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, acetyl ricinolic acid Methyl, acetyl tributyl citric acid, polyethylene glycol, dibutyl diglycol succinate, bis (butyl diglycol) adipate, bis (methyl diglycol) adipate and the like. To illustrate a specific trade name, PL-O12, PL-O19, PL-320, PL-710, actor series (M-1, M-2, M-3, M-) manufactured by Riken Vitamin Co., Ltd. 4, M-107FR): manufactured by Taoka Chemical Co, Ltd. ATBC: produced by Daihachi Chemical Industry Co., Ltd. BXA, MXA: Taiyo Kagaku Co. The chirabazole VR-01, VR-05, VR-10P, VR-10O1, VR-623 etc. which were manufactured by Ltd. are mentioned.

The compounding quantity or content of a plasticizer (D) needs to be 0.5-10 mass%, and, as for the sum total of polylactic acid-type resin (A) and a plasticizer (D), it is preferable that it is 1-5 mass%. If it is less than 0.5 mass%, an effect will be inadequate, and if it exceeds 10 mass%, the crystallinity degree of a molded article will become high and heat resistance will fall.

Specific examples of the peroxide (B) used in the present invention include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valate, dicumylfur Oxide, butyl peroxy benzoate, dibutyl peroxide, bis (butyl peroxy) diisopropyl benzene, dimethyl di (butyl peroxy) hexane, dimethyl di (butyl peroxy) hexyne, butyl peroxy cumene, etc. are mentioned. . The compounding quantity of a peroxide (B) is 100 mass parts with respect to 100 mass parts of polylactic acid-type resins (A), or 100 mass parts of polylactic acid-type resins (A) and a plasticizer (D) (Hereafter, a polylactic acid-type resin (A) and a plasticizer ( It is necessary that it is 0.01-10 mass parts with respect to "the polylactic acid-type resin composition" which mix | blended D). Preferably it is 0.1-5 mass parts. Although it can use even if it exceeds 10 mass parts, the effect is not only saturated but it is not economical. Moreover, since such a peroxide decomposes and is consumed at the time of mixing with resin, even if it is used at the time of mixing | blending, it may not remain in the obtained resin composition. By mix | blending a peroxide, a polylactic acid-type resin component crosslinks and for this reason, the mechanical strength, heat resistance, and dimensional stability of the obtained resin composition improve.

The silane compound (C) having two or more functional groups selected from the alkoxy group, the acryl group, the methacryl group, and the vinyl group used in the present invention is used as a crosslinking aid for the polylactic acid-based resin (A). Although it contributes to the increase of the crystallization rate of system resin (A), it is represented by following formula (1).

In Formula (1), at least 2 or more of R <1> -R <4> represents the functional group selected from an alkoxy group, an acryl group, a methacryl group, a vinyl group, or a substituent which has these functional groups. Remainder shows other than an alkoxy group, a vinyl group, and an acryl group, for example, hydrogen, an alkyl group, and an epoxy group are mentioned. As an alkoxy group, a methoxy group and an ethoxy group are mentioned, for example. As a substituent which has a vinyl group, a vinyl group and p-styryl group are mentioned, for example. As a substituent which has an acryl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, etc. are mentioned, for example. Examples of the alkyl group include methyl group and ethyl group. As a substituent which has an epoxy group, 3-glycidoxy propyl group, 2- (3, 4- epoxycyclohexyl) group, etc. are mentioned, for example.

Examples of detailed examples and trade names of such silane compounds (C) include tetramethoxy silane (TSL8114 manufactured by GE Toshiba Silicone Co., Ltd., KBM-04 manufactured by Shin-Etsu Chemical Co., Ltd.). ), Tetraethoxy silane (TSL8124 manufactured by GE Toshiba Silicone Co., Ltd., KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd.), methyltrimethoxy silane (GE Toshiba Silicone Co. , TSL8113 produced by Ltd., KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.), methyltriethoxy silane (TSL8123 manufactured by GE Toshiba Silicone Co., Ltd.), Shin-Etsu KBE-13 manufactured by Chemical Co., Ltd., dimethyldimethoxy silane (TSL8112 manufactured by GE Toshiba Silicone Co., Ltd.), and dimethyldiethoxy silane (GE Toshiba Silicone Co., Ltd.) TSL8122, KBE-22 manufactured by Shin-Etsu Chemical Co., Ltd., methyldimethoxy silane (made by GE Toshiba Silicone Co., Ltd.) TSL8117), methyldiethoxy silane (TSL8127 made by GE Toshiba Silicone Co., Ltd.), phenyltrimethoxy silane (TSL8173 made by GE Toshiba Silicone Co., Ltd.), phenyltriethoxy silane ( TSL8178 manufactured by GE Toshiba Silicone Co., Ltd., KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.), diphenyldimethoxy silane (made by GE Toshiba Silicone Co., Ltd.) TSL8172), diphenyldiethoxy silane (TSL8177 manufactured by GE Toshiba Silicone Co., Ltd.), hexyltrimethoxy silane (KBM-3063 manufactured by Shin-Etsu Chemical Co., Ltd.), decyl tree Methoxy silane (KBM-3103C manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyldimethoxymethyl silane (TSL-8355 manufactured by GE Toshiba Silicone Co., Ltd.), 3-glycidoxypropyltrimethoxy silane (TSL-8350 manufactured by GE Toshiba Silicone Co., Ltd., KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) ), Dimethylvinylmethoxy silane (TSL8317 made by GE Toshiba Silicone Co., Ltd.), methylvinyldimethoxy silane (TSL8315 made by GE Toshiba Silicone Co., Ltd.), methylvinyldiethoxy silane ( TSL8316 manufactured by GE Toshiba Silicone Co., Ltd.), dimethylvinylethoxy silane (TSL8318 manufactured by GE Toshiba Silicone Co., Ltd.), vinyl trimethoxy silane (Shin-Etsu Chemical Co., Ltd) KBM-1003 manufactured by.), Vinyltriethoxy silane (TSL8311 manufactured by GE Toshiba Silicone Co., Ltd., KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxy silane (Shin-Etsu Chemical Co. , KBE-402 manufactured by Ltd., p-styryltrimethoxy silane (KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyl Methoxy silane (TSL8375 manufactured by GE Toshiba Silicone Co., Ltd., KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxy silane (GE Toshiba Silicone) TSL8370 manufactured by Co., Ltd., KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxy silane (Shin-Etsu Chemical Co., Ltd.) KBE-502), 3-methacryloxypropyltriethoxy silane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropyltrimethoxy silane (Shin-Etsu KBM-5103 produced by Chemical Co., Ltd.), 3-acryloxypropylmethyldimethoxy silane (KBM-5102 produced by Shin-Etsu Chemical Co., Ltd.), and the like.

Especially, the silane compound which has one functional group chosen from an acryl group, a methacryl group, and a vinyl group, and has three alkoxy groups is preferable at the point of the improvement of a crystallization rate. Examples of specific examples and trade names of such silane compounds include vinyltrimethoxy silane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) and vinyltriethoxy silane (GE Toshiba Silicone Co., Ltd.). Manufactured by TSL8311, KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., p-styryltrimethoxy silane (KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.) , 3-methacryloxypropyltrimethoxy silane (TSL8370 manufactured by GE Toshiba Silicone Co., Ltd., KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl Triethoxy silane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropyltrimethoxy silane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) And the like.

The compounding quantity or content of a silane compound (C) needs to be 0.01-5 mass parts with respect to 100 mass parts of polylactic acid-type resin (A), or 100 mass parts of polylactic acid-type resin composition mentioned above, Preferably it is 0.02- 3 mass parts, More preferably, it is 0.05-1 mass part. If it is less than 0.01 mass part, the effect of addition is not confirmed. Although it can be used in excess of 5 parts by mass, the effect is not only saturated but not economical.

As the nucleating agent (E) used in the present invention, an organic amide compound, an organic hydrazide compound, a carboxylic acid ester compound, an organic sulfonate salt, a phthalocyanine compound, a melamine compound and an organic phosphone in terms of its crystallization promoting effect One or more selected from acid salts may be listed.

As an organic amide compound or an organic hydrazide compound, ethylenebisoleic acid amide, methylenebisacrylic acid amide, ethylenebisacrylic acid amide, hexamethylenebis-9,10-dihydroxystearic acid bisamide, p- Xylylenebis-9,10-dihydroxystearic acid amide, decanedicarboxylic acid dibenzoylhydrazide, hexanedicarboxylic acid dibenzoylhydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 2,6-naphthalenedicarboxylic acid dianilide, N, N ', N "-tricyclohexyltrimesinic acid amide, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid di Anilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N'-dibenzoyl-1,4-diaminocyclohexane, N, N'-dicyclohexanecarbonyl-1,5-diamino Naphthalene, ethylenebisstearic acid amide, N, N'-ethyl Lenbis (12-hydroxystearic acid) amide, octanedicarboxylic acid dibenzoylhydrazide, etc. Among them, N, N ', N "-tricyclohexyl tree in view of dispersibility and heat resistance in the resin. Mesic acid amide, N, N'-ethylenebis (12-hydroxystearic acid) amide, and octanedicarboxylic acid dibenzoylhydrazide are preferred.

Examples of the carboxylic acid ester compound include monocarboxylic acid esters, ethylene glycol monoesters and ethylene glycol diesters, glycerin monoesters, glycerin diesters, and glycerin triesters, and various kinds can be used. Specific examples include lauric acid cetyl ester, stearic acid cetyl ester, monolauric acid glycol, monostearic acid glycol, dilauric acid glycol, dipalmitic acid glycol, distearic acid glycol, monolauric acid glycerine ester, monostearic acid glycerine ester, Dilauric acid glycerin ester, distearic acid glycerin ester, trilauric acid glycerin ester, tristearic acid glycerin ester and the like.

As the organic sulfonate, various ones such as sulfoisophthalate can be used. Among them, 5-sulfoisophthalic acid dimethyl metal salt is preferable in view of crystallization promoting effect. In addition, barium salt, calcium salt, strontium salt, potassium salt, rubidium salt, sodium salt and the like are preferable, and in particular, 5-sulfoisophthalic acid dimethyl potassium and 5-sulfoisophthalate dimethyl barium are preferable.

Although various things can be used as a phthalocyanine type compound, it is preferable to use a mutant metal complex, and especially, copper phthalocyanine is preferable at the point of a crystallization promoting effect.

Although various things can be used as a melamine type compound, it is preferable to use melamine cyanurate from the point of a crystallization promoting effect.

As an organic phosphonic acid compound, phenyl phosphonate is preferable at the point of a crystallization promoting effect. Among them, zinc phenyl phosphonate is particularly preferable.

As nucleating agent, these can be mix | blended or contained individually or in combination of 2 or more types.

You may use together various types of inorganic nucleating agents with respect to these organic nucleating agents.

When the compounding quantity or content of crystal nucleating agent (E) is 100 mass parts of polylactic acid-type resin (A) or polylactic acid-type resin composition, it is preferable that it is 0.03-5 mass parts, More preferably, it is 0.1-4 mass parts. If it is less than 0.03 mass part, the effect of a mixing | blending or containing is insufficient. On the other hand, if it exceeds 5 parts by mass, the effect as a nucleating agent is saturated and not only economically disadvantageous, but also the environmental residue is not preferable because the residue after biodegradation increases.

Examples of the fibrous reinforcing material (F) used in the present invention include glass fibers, carbon fibers, alumina fibers, kenaf fibers, wollastonite, potassium titanate, cellulose fibers, metal fibers, metal whiskers, ceramic whiskers, and the like. In particular, an inorganic fibrous reinforcing material tends to contribute to the improvement of strength and rigidity. The reason for this is presumably because the adhesion to the resin is increased by the reaction between the silane compound (C) and the fibrous reinforcing material (F). Glass fiber is preferable at hot rigidity, strength, and economy, and glass fiber which has a flat cross section is more preferable at the point of impact strength.

Glass fibers having a flat cross section are produced by known methods for producing glass fibers and focused by a bundling agent, and are used in the form of chopped strands where the bundled glass fiber strands are collected and cut into a constant length. The focusing agent contains at least one type of coupling agent such as a silane coupling agent, a titanium coupling agent, a zirconia coupling agent, etc., an antistatic agent, a film forming agent, or the like for improving the adhesion to the matrix resin and the uniform dispersibility. It is suitable for the former resin. Known binding agents can be used as such binding agents.

It is preferable that the glass fiber which has a flat cross section is 10-50 micrometers in fiber cross section, It is more preferable that it is 15-40 micrometers, It is especially preferable that it is 20-35 micrometers. The flat cross section preferably has a long diameter / short diameter ratio of 1.5 to 10, and more preferably 2.0 to 6.0. If the long diameter / short diameter ratio is less than 1.5, the effect of making the cross section flat is small, and the glass fibers of more than 10 are difficult to manufacture themselves. Moreover, it is preferable that the ratio (aspect ratio) of the average fiber length and average fiber diameter of this glass fiber is 2-120, It is more preferable that it is 2.5-70, It is especially preferable that it is 3-50. When the ratio between the fiber length and the average fiber diameter is less than 2, the effect of improving mechanical strength is small. When the ratio of the fiber length to the average fiber diameter exceeds 120, the anisotropy becomes large and the appearance of the molded product deteriorates. The average fiber diameter of the glass fiber which has such a flat cross section means the number average fiber diameter at the time of converting a flat cross-sectional shape into the round shape of the same area. As glass fiber which has a flat cross section, the fiber of general glass composition like E glass is used preferably. However, any composition can be used as long as it can be made of glass fiber and is not particularly limited.

In the resin composition of this invention, it is preferable to use a polyhydric carbodiimide compound (G) together with a fibrous reinforcing material (F) for strength improvement and wet heat durability improvement. Epoxy compounds, oxazoline compounds, and monocarbodiimide compounds which are other compounds are generally effective in improving the wet heat durability of polylactic acid. However, with respect to the present invention, there is no effect as much as the polyhydric carbodiimide compound (G) in terms of strength improvement and wet heat improvement. However, when using a polyhydric carbodiimide compound (G), you may use together another epoxy compound, an oxazoline compound, and a mono carbodiimide compound.

The polyhydric carbodiimide compound (G) used for this invention is a compound which has two or more carbodiimide groups in one molecule, 1,5-naphthalene carbodiimide, 4,4'- diphenylmethane carbodiimide, 4 , 4'-diphenyldimethylmethane carbodiimide, 1,3-phenylene carbodiamide, 1,4-phenylene diisocyanate, 2,4-tolylene carbodiimide, 2,6-tolylene carbodiimide , A mixture of 2,4-tolylene carbodiimide and 2,6-tolylene carbodiimide, hexamethylene carbodiimide, cyclohexane-1,4-carbodiimide, xylylene carbodiimide, isophoronecar Bodyimide, dicyclohexylmethane-4,4'-carbodiimide, methylcyclohexane carbodiimide, tetramethylxylylene carbodiimide, 2,6-diisopropylphenyl carbodiimide, 1,3,5 -Triisopropyl benzene-2,4-carbodiimide etc. are mentioned.

Such a carbodiimide compound (G) can be manufactured by the method known conventionally, and can be manufactured by the carbodiimide reaction accompanying the decarbonation reaction which uses a diisocyanate compound as a raw material. An isocyanate group may remain | survive and the terminal of a molecule | numerator may be sealed by monoisocyanate.

As a detailed trade name of the polyhydric carbodiimide compound (G), for example, HMV-8CA produced by Nisshinbo Inc., LA-1: Stabazole P produced by Rhein Chemie Ltd., and Starbazole P100 are listed.

The compounding quantity or content of a fibrous reinforcing material (F) and a polyhydric carbodiimide compound (G) is 39.9-89.9 mass% of polylactic acid-type resin (A), a peroxide (B), a silane compound (C), and a plasticizer (E) in total. It is preferable that it is 60-10 mass% of fibrous reinforcement materials (F) or 0.1-10 mass% of polyhydric carbodiimide compound (G). However, in total, it is 100 mass%.

When the compounding quantity or content of fibrous reinforcing material (F) is less than 10 mass%, hot rigidity may become low, and when it exceeds 60 mass%, a manufacturing problem may arise. When the compounding quantity or content of a polyhydric carbodiimide compound (G) is less than 0.1 mass%, there exists a tendency for the intensity | strength of a resin composition to fall, and when more than 10 mass%, the heat resistance of a resin composition may fall.

The thermoplastic resin composition of this invention can be used suitably also for the electrical appliance component which requires the performance of both a flame retardance performance and a thin strength by mix | blending or containing a flame retardant (H).

As a flame retardant (H) used for this invention, a phosphorus flame retardant, a silicone flame retardant, and an inorganic flame retardant are mentioned, You may use 2 or more types together.

The compounding quantity or content of a flame retardant (H) is 36.9-89.9 mass% in total of polylactic acid-type resin (A), a peroxide (B), a silane compound (C), and a plasticizer (E), and a polyhydric carbodiimide compound (G) 0.1- It is preferable that it is 3-30 mass% with respect to 10 mass%. However, in total, it is 100 mass%.

When the compounding quantity or content of a flame retardant (H) is less than 3 mass%, a flame retardant performance is hardly expressed. On the other hand, when the compounding quantity or content of a flame retardant (H) exceeds 30 mass%, there exists a tendency for the intensity | strength of a resin composition to fall.

The flame retardant (H) is particularly preferably a phosphinic acid metal salt, polyphosphoric acid melamine, melamine cyanurate or condensed phosphate ester in view of enhancing the flame retardant effect.

MELAPUR series (MELAPUR 200/70) manufactured by Ciba Specialty Chemicals as a specific trade name of melamine polyphosphate: MPP series manufactured by Nippon Carbide Industries Co., Inc. (formerly Sanwa Chemical Co., Ltd.) MPP-A, MPP-B): PMP series (PMP-100, PMP-200, PMP-300) produced by Nissan Chemical Industries, Ltd., etc. are mentioned. As a specific brand name of melamine cyanurate, MC series manufactured by Nissan Chemical Industries, Ltd .: MELAPUR series (MELAPUR MC-25) produced by Ciba Specialty Chemicals, etc. are mentioned. Specific examples of the condensed phosphate ester include PX-200, PX-201, PX-202, CR-733S, CR-741, CR747 and the like produced by Daihachi Chemical Industry Co., Ltd. Specific examples of the phosphinic acid metal salt include OP series (OP 930, OP 935, OP 1230, OP 1312, OP 1240, etc.) manufactured by Clariant.

A pigment, a heat stabilizer, an antioxidant, a weather agent, a light agent, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a filler, a crystal nucleus material, etc. can be added to the resin composition of the present invention within a range that does not significantly impair its properties. Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, halides of alkali metals, and vitamin E. As inorganic fillers, talc, calcium carbonate, zinc carbonate, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, Zeolites, hydrotalcites, gold, boron nitride, graphite. Examples of the organic fillers include natural polymers such as starch, cellulose fine particles, wood flour, bean curd, rice husk, bran, and modified substances thereof. Talc, kaolin, etc. are mentioned as an inorganic nucleus material. Examples of the organic nucleus material include sorbitol compounds, benzoic acid and metal salts of the compounds, phosphate ester metal salts, and rosin compounds.

Peroxide (B), silane compound (C), fibrous reinforcing material (F), polyvalent carbodiimide compound (G), plasticizer (D), flame retardant (H), crystal nucleating agent (E), to polylactic acid resin (A), As a means of mix | blending another additive, the method of melt-kneading using a general extruder is mentioned. It is preferable to use a twin screw extruder in the sense of improving the kneaded state. The kneading temperature is preferably in the range of (melting point of polylactic acid-based resin (A) + 5 ° C) to (melting point of polylactic acid-based resin (A) + 100 ° C), and the kneading time is preferably 20 seconds to 30 minutes. If it is lower than this range or short time, kneading | mixing and reaction will become inadequate, and if it is high temperature or long time, resin decomposition or coloring may occur.

At the time of blending, the polylactic acid-based resin (A), the plasticizer (D), and the nucleating agent (E) are preferably added simultaneously from the top feeder of the extruder as far as possible so as to be sufficiently compatible or dispersed. Peroxide (B) may be added when the polylactic acid resin (A) and the plasticizer (D) are sufficiently compatible with each other, or when the polylactic acid resin (A) is in a molten state and reacted with the polylactic acid resin (A). Since it is preferable, the method of adding in the middle from the barrel of an extruder is preferable. When the fibrous reinforcing material (F) is melt-kneaded together with the polylactic acid resin (A) and the plasticizer (D), the fiber may be broken and the strength may be lowered. Thus, the polylactic acid resin (A) is similar to the peroxide (B). ) And the plasticizer (D) and the like are preferably melt-kneaded and added from the middle of the barrel as a side feed.

As a preferable method in the case of adding a peroxide (B) from the middle of a barrel, the method of melt | dissolving or disperse | distributing a peroxide (B) to a medium and injecting into a kneader is mentioned. Thereby, operability can be improved especially. Specifically, the polylactic acid-based resin (A), the plasticizer (D), and the crystal nucleating agent (E) can be melt kneaded by injecting a solution or dispersion of the peroxide (B) during melt kneading. The silane compound (C) may be added from the top feeder together with the polylactic acid resin (A), the plasticizer (D), and the crystal nucleating agent (E). When a silane compound (C) is melt | dissolved or disperse | distributed to the dissolution liquid or dispersion liquid of a peroxide (B), the method of inject | pouring this from a middle with peroxide (B) is also preferable if there is no problem in operation.

As a medium for dissolving or dispersing the peroxide (B), a general one can be used. Especially, the plasticizer which is excellent in compatibility with polylactic acid-type resin (A) is preferable, and if a peroxide (B) melt | dissolves or disperse | distributes uniformly, the same thing as the plasticizer (D) used for this invention may be used, and a different thing may be used Also good. Moreover, you may use together 2 or more types of plasticizers. As for the mass ratio of a peroxide (B) and a medium, a peroxide (B): medium = 1: 0.5-1: 20 are preferable, and 1: 1-1: 5 are optimal.

The addition procedure of the peroxide (B) and the fibrous reinforcing material (F) into the extruder will be described. The peroxide (B) needs to react with the polylactic acid-based resin (A), and in order to react efficiently, it is necessary to pass the kneading screw portion in the extruder. On the other hand, it is preferable to add fibrous reinforcement F from downstream than a kneading screw part, in order to suppress breaking of a fiber.

Although the compounding order of a carbodiimide compound (G) and a flame retardant (H) is not specifically limited, What is necessary is just to select a top feed addition method, an intermediate addition method, etc. suitably in consideration of dispersibility, reactivity, and thermal stability. Moreover, the carbodiimide compound (G) and the flame retardant (H) are mix | blended at high concentration, and the resin composition pellets melt-kneaded are produced, and the carbodiimide compound (G) and flame retardant (H) are mix | blended separately at low concentration. One resin composition or the resin composition pellet which is not mix | blended is created, these several types of pellets may be mixed, and the following injection molding and extrusion molding may be performed so that each component may finally be in the range prescribed | regulated by this invention.

The resin composition of this invention can be made into various molded objects by shaping | molding methods, such as injection molding, blow molding, extrusion molding, inflation molding, etc., or by shaping | molding methods, such as vacuum shaping | molding, pressure forming, and vacuum pressure forming after sheet processing. In particular, it is preferable to employ the injection molding method. In addition to the general injection molding method, a gas injection molding method, an injection press molding method, or the like can also be employed. Although it is injection molding conditions suitable for the resin composition of this invention, it is suitable to make cylinder temperature into 180-240 degreeC, More preferably, it is 190-230 degreeC. The mold temperature is preferably 140 ° C or lower. If the molding temperature is too low, the operability is likely to be unstable or overloaded, such as a short in the molded article. On the contrary, when molding temperature is too high, problems, such as the intensity | strength of the molded object obtained by decomposing | disassembling a resin composition, falling, or coloring may arise.

The resin composition of this invention can improve the heat resistance by promoting crystallization. As a method for this purpose, for example, there is a method of promoting crystallization by cooling in a mold during injection molding. In that case, it is preferable to cool mold temperature as crystallization temperature +/- 20 degreeC of a resin composition for predetermined time. In consideration of releasability, after that, the mold temperature may be lowered to the glass transition temperature or lower of the resin composition, and then the mold may be opened to take out the molded article. It is preferable to heat-treat the obtained molded article again to crystallization temperature +/- 20 degreeC as a method of promoting crystallization after molding. When two or more crystallization temperatures exist, the same process may be performed at each temperature and the crystallization temperature with the highest heat resistance may be selected. In the case where there are a plurality of glass transition temperatures, a glass transition temperature without problem may be selected.

Specific examples of the molded article include resin parts for telephone products such as various casing bodies such as personal computers, printers, projector lamps, and the like: resin parts for automobiles such as bumpers, inner panels and door trims. Moreover, a film, a sheet, a hollow molded article, etc. can also be obtained.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.

1. Evaluation item

(1) Melt Flow Rate (MFR)

According to ISO standard 1133, it measured at 190 degreeC and the load 21.2N.

(2) Heat deflection temperature (DTUL)

In accordance with ISO 75-1 and -2 standards, the heat deflection temperatures were measured at 0.45 MPa load in Examples 1 to 15 and Comparative Examples 1 to 4, and at 1.8 MPa in Examples 16 to 37 and Comparative Examples 5 to 15, respectively. . It is preferable that heat distortion temperature is 80 degreeC or more practically.

(3) forming cycle

The molding test of the dumbbell type test piece was implemented by the injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.). After the resin was filled into the mold under the conditions of a molding temperature of 190 ° C. and a mold temperature of 100 ° C., a cooling cycle was gradually extended to evaluate a molding cycle in which mold release was improved. However, when mold release did not become good even in 60 second, it did not evaluate in more time. It is preferable that a cooling time is 40 second or less from an economic point of view.

(4) flexural strength

It measured according to the standard of ISO 178. It is preferable that flexural strength is 180 Mpa or more practically.

(5) flexural modulus

It measured according to ISO 178 standard. It is preferable that a bending elastic modulus is 9.0 GPa or more practically.

(6) flame retardant

It was measured according to the vertical combustion test method of UL 94 (standard defined by Under Writers Laboratories Inc.). In addition, the thickness of the test piece was 1/16 inch (about 1.6 mm). It is preferable that flame retardance is V-2, V-1, or V-0, and it is especially preferable that it is V-1, V-0.

2. Raw material

(1) polylactic acid-based resin

Nature Works 3001D produced by Cargilldow: MFR 10 g / 10 min, melting point 168 ° C. (hereinafter abbreviated as “PLA”).

(2) polybutylene succinate resin

GS-Pla AZ-71T produced by Mitsubishi Chemical Corporation: MFR 20g / 10min (hereinafter abbreviated as "PBS").

(3a) plasticizer

Glycerindiacetomonocaprate: PL-019 manufactured by Riken Vitamin Co., Ltd.

(3b) plasticizer

Medium chain fatty acid triglycerides: Ecter-M-1, manufactured by Riken Vitamin Co., Ltd.

(3c) plasticizer

Polyglycerin Fatty Acid Ester: Taiyo Kagaku Co. Chirabazole VR-O1 produced by Ltd.

(3d) plasticizer

Tributyl acetylcitrate: ATBC manufactured by Taoka Chemical Co, Ltd.

(3e) plasticizer

Trinormaloctyl trimellitate: Trimax N-O8 produced by Kao Corporation.

(4) peroxide

Di-t-butylperoxide: per-butyl D prepared by NOF Coporation.

(5a) Silane Compound

Vinyltrimethoxy silane: KBM-1003 produced by Shin-Etsu Chemical Co., Ltd. (hereinafter abbreviated as "S1").

(5b) silane compound

3-acryloxypropyltrimethoxy silane: KBM-5102 produced by Shin-Etsu Chemical Co., Ltd. (hereinafter abbreviated as "S2").

(5c) silane compound

p-styryltrimethoxy silane: KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter abbreviated as "S3").

(5d) silane compound

3-methacryloxypropyltrimethoxy silane: TSL8370 manufactured by GE Toshiba Silicone Co., Ltd. (hereinafter abbreviated as "S4").

(6) acrylic ester compound (crosslinking agent)

Ethylene Glycol Dimethacrylate: Blemmer-PDE-50 manufactured by NOF Corporation.

(7a) polyhydric carbodiimide compounds

LA-1 produced by Nisshinbo Inc. (hereinafter abbreviated as `` CC1 '')

(7b) polyhydric carbodiimide compounds

Stabacsol P produced by Rhein Chemie Ltd. (hereinafter abbreviated as "CC2").

(7c) monocarbodiimide compound

Stabacsol I (hereinafter abbreviated as "CC3") produced by Rhein Chemie Ltd.

(7d) epoxy compound

Phenylglycidyl ether: Denacol EX-141 produced by Nagase Chemtex Corporation (hereinafter abbreviated as "EC").

(8a) glass fiber having a circular cross section

O3JFAT592 produced by Owens Corning Corporation, fiber diameter φ10 μm, fiber length 3 mm (hereinafter abbreviated as “GF1”).

(8b) glass fiber with flat cross section

CSG3PA820S produced by Nitto Boseki Co., Ltd., 28 µm long diameter, 7 µm short diameter, flat glass fiber having a flat section with a ratio of 4.0, and a fiber length of 3 mm (hereinafter abbreviated as "GF2").

(8c) kenaf fiber

Kenaf cut to a constant length of about 5 mm is pulverized with a turbo mill (T-250 manufactured by Matsabo Corporationdp), unwrapped, and has a diameter of 20 to 50 µm and a fiber length of 1 to 5 mm (hereinafter abbreviated as "KF"). box).

(9a) flame retardant

Phosphate metal salt: Exolite OP935 (hereinafter abbreviated as "FR1") manufactured by Clariant.

(9b) flame retardant

Condensed Phosphate Ester Resorcinolbis (Dixylenyl Phosphate): PX-200 (hereinafter abbreviated as "FR2") produced by Daihachi Chemical Industry Co., Ltd.

(10) organic nucleating agent

N, N ', N "-tricyclohexyltrimesinic acid amide: TF-1 produced by New Japan Chemical Co., Ltd. (hereinafter abbreviated as" CN ").

(1Ob) Organic Crystallization Agents

5-Sulfoisophthalic acid dimethyl potassium: produced by Takemoto Oil & Fat Co., Ltd. (hereinafter abbreviated as "5S-IPA").

(10O) Organic Nucleating Agent

5-Sulfoisophthalic acid dimethyl barium: Produced by Takemoto Oil & Fat Co., Ltd. (hereinafter abbreviated as "5S-IPB").

Examples 1-15, Comparative Examples 1-4

Polylactic acid-based resin (A), plasticizer (D), crystals from the top feeder using a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.) in the formulation shown in the top feed composition of Table 1. The nucleating agent (E) was supplied, and melt-kneading extrusion was performed at the processing temperature of 190 degreeC. At that time, the pump was used in the middle of the kneader, and the mixed solution of the peroxide (B) and the crosslinking aid was injected by the formulation shown in the middle composition of Table 1. Then, the discharged resin was cut into pellets to obtain a resin composition.

Subsequently, using the pellet which performed the drying process of 70 degreeC * 8h with a vacuum dryer, the dumbbell test piece was shape-molded with the injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.), and the crystallization rate was raised and lowered. Based on the evaluation, the molding cycle to be changed was evaluated. Moreover, the heat distortion temperature was measured using the test piece of 60 second of molding cycles. Table 1 summarizes the results of the various physical property evaluations.

Examples 1-15 are also good values of heat distortion temperature and a shaping | molding cycle. In contrast, Comparative Example 1 had a low heat deformation temperature because the proportion of the plasticizer was too large. In Comparative Examples 2 and 3, since the silane compound was not used as the crosslinking aid, the molding cycle was long and the heat deformation temperature was also low. In addition, in Comparative Example 4, since no peroxide was added, the thermal deformation temperature was low, the mold release was not good even in the molding cycle of 100 seconds, and the thermal deformation temperature was also low.

Examples 16-37

Using a twin screw extruder (TEM 26SS manufactured by Toshiba Machine Co., Ltd.), polylactic acid-based resins, carbodiimide compounds, and plasticizers were prepared from the top feeder by the formulations shown in the top feed compositions of Tables 2 and 3. In the case of use, a plasticizer and a nucleating agent were used, and in the case of using a nucleating agent, melt kneading extrusion was performed at a processing temperature of 190 ° C. At that time, the mixed solution of a silane compound / peroxide / plasticizer (used as a solvent) was inject | poured in the formulation shown in addition composition 1 of Table 2 and Table 3 using a pump in the middle of a kneading machine. From the downstream, when a fibrous reinforcement agent and a flame retardant were used in the ratio shown in the addition composition 2 on the downstream side, a flame retardant was supplied from a side feed. Then, the discharged resin was cut into pellets to obtain a resin composition.

Subsequently, using a pellet subjected to drying treatment at 80 ° C. × 8 h with a vacuum dryer, a molding test of the dumbbell test piece was performed by an injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.) to evaluate the molding cycle. did. In addition, the heat deformation temperature, the bending strength, and the bending elastic modulus were measured using a test piece having a molding cycle of 60 seconds.

In Examples 31, 32, and 33 incorporating a flame retardant, a UL test piece having a thickness of 1.6 mm was produced by an injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.), and a UL combustion test was performed.

The results are shown in Tables 2 and 3.

Comparative Examples 5-11

When using a twin screw extruder (TEM 26SS manufactured by Toshiba Machine Co., Ltd.) and using polylactic acid resin, carbodiimide compound, and plasticizer from the top feeder in the formulation shown in the top feed composition of Table 4. In the case of using a plasticizer and a nucleating agent, melt kneading extrusion was performed at a processing temperature of 190 ° C by supplying a nucleating agent. At that time, a mixed solution of a silane compound / peroxide / plasticizer (used as a solvent) was injected in the formulation shown in the addition composition 1 in Table 4 using a pump in the middle of the kneader. On the downstream side further, when using a fibrous reinforcement agent and a flame retardant in the ratio shown in addition composition 2 in the middle of Table 4, a flame retardant was supplied from a side feed. Then, the discharged resin was cut into pellets to obtain a resin composition.

However, regarding the comparative example 11, since the compounding quantity of glass fiber was too much, a strand fell into pieces and it could not pelletize.

Subsequently, using a pellet subjected to drying treatment at 80 ° C. × 8 h with a vacuum dryer, a molding test of the dumbbell test piece was performed by an injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.) to evaluate the molding cycle. did. In addition, the heat deformation temperature, the bending strength, and the bending elastic modulus were measured using a test piece having a molding cycle of 60 seconds.

Table 4 shows the results of various physical property evaluations.

Examples 16-37 showed the favorable value with heat distortion temperature, molding cooling time, bending strength, and bending elastic modulus.

Since the comparative example 5 and the comparative example 12 did not mix | blend a silane compound, the molding cycle was too long.

Since the comparative example 6 did not mix | blend peroxide, molding cooling time was long and heat distortion temperature was low. Moreover, flexural strength was also low.

Since Comparative Examples 7-9 did not use a polyhydric carbodiimide compound, they had low bending strength.

Since the compounding quantity of the glass fiber was too small, the comparative example 10 had the low degree of improvement of the bending strength and the bending elastic modulus by mix | blending a glass fiber.

In the comparative example 11, since the compounding quantity of the glass fiber was too large as mentioned above, the strand of resin which came out from the extruder nozzle was fragmented, and pellet sampling was not possible, and operability was bad.

Since the compounding quantity of the plasticizer was too large, the comparative example 13 had low flexural strength and flexural modulus.

Since the compounding quantity of polyhydric carbodiimide was too much in the comparative example 14, heat resistance fell and the molding cooling time was also long.

Comparative Example 15 had a low bending strength because the amount of the flame retardant was too large.

Claims (12)

0.01-5 parts by mass of a polylactic acid resin or a polylactic acid-based resin composition, 0.01 to 10 parts by mass of a peroxide, 0.01 to 5 parts by mass of a peroxide, and a silane compound having two or more functional groups selected from an alkoxy group, an acryl group, a methacryl group, and a vinyl group. It is obtained by mix | blending, The thermoplastic resin composition characterized by the above-mentioned. The method of claim 1,
The said polylactic acid-type resin composition contains 90 to 99.5 mass% of polylactic acid-type resins, and 0.5 to 10 mass% of plasticizers. The method of claim 2,
The plasticizer is a thermoplastic resin composition, characterized in that at least one selected from aliphatic polyhydric carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, aliphatic polyether polyhydric carboxylic acid ester derivatives. The method of claim 1,
A thermoplastic resin composition comprising at least one selected from organic amide compounds, organic hydrazide compounds, carboxylic acid ester compounds, organic sulfonates, phthalocyanine compounds, melamine compounds and organic phosphonates as crystal nucleating agents. . The method of claim 4, wherein
The nucleating agent is a 5-sulfoisophthalic acid dimethyl metal salt, N, N ', N "-tricyclohexyltrimesic acid amide, N, N'-ethylenebis (12-hydroxystearic acid) amide, octane dicarboxylic acid At least one member selected from dibenzoylhydrazide is a thermoplastic resin composition. The method of claim 1,
The polylactic acid-based resin is a thermoplastic resin composition, characterized in that the polylactic acid as a main component. The method of claim 1,
The polylactic acid-based resin is a thermoplastic resin composition, characterized in that made of a plant-based raw material. 100 mass% of the whole is contained, and it contains 39.9-99.9 mass% of thermoplastic resin compositions of Claim 1, 60-10 mass% of fibrous reinforcement materials, and 0.01-10 mass% of polyhydric carbodiimide compounds, It is characterized by the above-mentioned. Thermoplastic resin composition. The method of claim 8,
The fibrous reinforcing material is a thermoplastic resin composition, characterized in that the glass fiber having a flat cross section. 100 mass% as a whole, 36.9-86.9 mass% of the thermoplastic resin composition of Claim 1, 10-60 mass% of fibrous reinforcement materials, 3-30 mass% of flame retardants, and 0.1-10 mass% of polyhydric carbodiimide compounds A thermoplastic resin composition, characterized in that it contains. The method of claim 10,
The fibrous reinforcing material is a thermoplastic resin composition, characterized in that the glass fiber having a flat cross section. A molded article characterized by molding the thermoplastic resin composition according to claim 1.